Cyan component for diazotype color process



Patented Jan. 17,1950

'ATENT. .OFFICE CYAN COMPONENT FOR DIAZOTYPE COLOR PROCESS seal 6. siiikin and Thaddeus a. Trojnar, Binghamton, N. Y., assignors to General Aniline & Film Corporation, New York, N. 'Y., a corporation of Delaware No. Drawing. Application June 6, 194 7,

. Serial No. 753,036

4 Claims.

The present invention relates to sensitized diazotype materials'for the diazotype color process which when exposed through a cyan separation positive and developed yield greenish blue images of high intensity.

It has been suggested that the diazotype process be utilized for the purpose of manufacturing natural color prints. The method suggested involved printing separation positives in the primary colors on separate transparent plastic film layers, dryedeveloping the layers and transposing the layers in register to produce a color print.

This process, howeven'was found to be unsatisfactory primarily because the sensitized compositions used for producing the cyan records yielded images too blue in color. Inasmuch as the cyan record is the key image record just as in color photography the decided blue nature of this record led to color distortion. This phenomenon which also manifests itself in three-color photography as may be seen from Frohlich et al. U. S. Patent No. 2,357,394; militated against the adoption of the aforementioned process despite the simplicity inherent therein.

We have now discovered that the objections referred to above can be completely avoided and cyan records blue-green in color and of high intensity can beobtained if there can be used as A the coupling component for the layer in which the cyan separation is to be recorded a l-hydroxy-naphthalene sulfonic acid containing in the 8-position a hydroxyl group or an aminoor substituted amino group. The employment of such coupling components in the sensitizingcompositions used to produce the cyan records in the diazotype color process and the processing of carriers bearing such com-positions constitute the purposes and. objects of thepresent invention.

The coupling components contemplated herein are typified by the following structural formula:

R OH

SOBH

in which R is hydroxyl, amino, acylamino, such as, acetylamino, propionylamino, butyrylamino, benzoylamino, and the like, alkylamino, such as,

2 methylamino, dimethylamino, ethylamino, diethylamino, and the like, or arylamino, such as, phenylamino, di-phenylamino, and the like.

Examples of compounds embraced by this formula and which we have found to be satisfactory for our purposes are:

acid acid acid 1 ydroxy n q qn e fl naphthalene i sulfonic acid ,1 hydroxy 3 benaoylamino naphthalene 'lsulfonic acid 1 hydroxy 8 methylamino naphthalene 5- sul-fonic acid 1 hydroxy 8 dimethylethylamino e naphthalene-G-sulfonic acid 1 hydroxy 8 butyrylamino naphthalene 5 sulfonic acid 1 hydroxy 8 phenylamino naphthalene 4- sulfonic acid The 1.S-dihydroxy-naphthalene sulfonic acids and the 1-hydroxy-8-aminonaphthalene sulfonic acids are well known compounds. The acyl derivatives mentioned above may be prepared by treatment of the 1-hydroxy-8-amino-naphthalene sulfonic acids with the anhydrides of the acids involved just as in the preparation of, for instance, acetyl J acid; Generally, the l-hydroXy-B-amino-naphthalene sulfonic acids in which the amino groupie substituted by alkyl or aryl may be prepared by alkylation and arylation, just as in the preparation of, for instance, dimethyl-2-amino-8-naphthol 6-su1fonic acid or of phenyl J acid.

The diazo component which is utilized in the sensitizing composition may be any of those generally employed in the diazo-type art although we prefer the N=substituted p-phenylenediamines. While the diazos are preferably employed in the form of the zinc chloride double salts they may likewise be utilized as such or in the form of their double salts with cadmium chloride, tin chloride or the like, or in the form of the fiuoro-borates or the alkyl or aryl sulfonates, such as, the methyl, ethyl, propyl, phenyl and the like sulfonates.

Examples of diazos which we have found to yield excellent results are those derived from the following compounds:

p-amino-N-diethyl-o-toluidine 4-diethylamino-o-phenetidine p- (N-ethyl-N-hydroxyethylamino) -o-to1uidine water or mixtures of water and a low molecular weight alcohol, 1. e., methyl alcohol, ethyl alcohol, and the like.

The base to which the sensitizing compositions are applied may be a sheet, film, or the like, of any transparent film-forming material preferably a cellulose ester, such as, cellulose acetate, cellulose propionate, cellulose acetate propionate, and the like.

The sensitized base is utilized in the manner outlined above, that is, by exposure under a desired cyan separation positive by U. V. light and development by ammonia fumes.

The following examples serve to illustrate the invention but it is to be understood that the invention is not restricted thereto:

Emample I A cellulose acetate film is coated with a solution of the following components:

Water 50 Alcohol 50 Citric acid grams Thiourea do 2 1.8-dihydroxy-naphthalene-4-sulfonic acid grams 2 The zinc chloride double salt of the diazo from 4-diethylamino-o-phenetidine grams 4 When dried and exposed to U. V. light under a selected cyan separation positive and developed in the usual way with ammonia vapor, a greenishblue positive reproduction of high density is obtained.

Example II Example III The procedure is the same as in Example I excepting that 1-hydroxy-8-acetylamino-naph- 55 thalene-4- sulf'onic acid is substituted for the dihydroxy-naphthalene sulfonic acid. Here again, the processing of the resulting film leads to greenish-blue positives of high density.

We claim:

1. Light sensitive diazotype material for use in producing a cyan record in the diazotype color process comprising a transparent base carrying as a light sensitive diazo compound a diazotized p-phenylene-diamine in which one of the amino groups is di-substituted by members selected from the class consisting of alkyl and hydroxyalkyl and as the azo component a compound of the following formula:

R OH

wherein R is a member selected from the class consisting of hydroxyl, amino, acylamino, alkylamino, and arylamino.

2. The article as defined in claim 1 in which the azo coupling component is 1.8-dihydroxynaphthalene-4-sulfonic acid.

3. The article as defined in claim 1 wherein the light sensitive diazo compound is the zinc chloride double salt of the diazo from 4-diethylaminoo-phenetidine and the azo coupling component is 1.8-dihydroxy-naphthalene-4-sulfonic acid.

4. The process of producing cyan diazotype prints capable of transmitting both green and blue light which comprises sensitizing a transparent base with a composition containing as a light sensitive diazo compound a diazotized p-phenylene-diamine in which one of the amino groups is di-substituted by members selected from the class consisting of alkyl and hydroxyalkyl and as a coupling component a compound of the following formula:

R OH

ammonia vapor.

SAM C. SLlFKlN. THADDEUS J. TROJNAR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,710,455 Langguth et al Apr. 23, 1929 2,375,366 Jacobus May 8, 1945 

1. LIGHT SENSITIVE DIAZOTYPE MATERIAL FOR USE IN PRODUCING A CYAN RECORD IN THE DIAZOTYPE COLOR PROCESS COMPRISING A TRANSPARENT BASE CARRYING AS A LIGHT SENSITIVE DIAZO COMPOUND A DIAZOTIZED P-PHENYLENE-DIAMINE IN WHICH ONE OF THE AMINO GROUPS IS DI-SUBSTITUTED BY MEMBERS SELECTED FROM THE CLASS CONSISTING OF ALKYL AND HYDROXYALKYL AND AS THE AZO COMPONENT A COMPOUND OF THE FOLLOWING FORMULA: 